Quaternary ammonium-functional silicon compounds

ABSTRACT

Quaternary ammonium-functional silicon compounds are prepared by reacting carboxylic acid-functional quaternary ammonium compounds with carbinol-functional silicon compounds. These quaternary ammonium-functional silicon compounds may be applied to textile materials to impart antistatic properties thereto.

This is a division of application Ser. No. 447,547, filed Dec. 7, 1982,now U.S. Pat. No. 4,511,727.

The present invention relates to quaternary ammonium compounds and moreparticularly to quaternary ammonium-functional silicon compounds andtheir use as antistatic agents for textile materials.

BACKGROUND OF THE INVENTION

Quaternary ammonium silicon compounds have been described, for example,in U.S. Pat. No. 3,471,541 to Morehouse, in which a tertiary amine isprepared by reacting an alkenyl ether of a tertiary hydroxypolyalkyleneoxy alkylamine with a hydrosilicon compound (i.e., a silaneor siloxane containing silicon-bonded hydrogen) in the presence of aplatinum catalyst. The resultant tertiary amines are then reacted withhydrocarbyl halides, monocarbylic acids or hydrocarbyl esters ofhaloalkanoic acids to form the corresponding quaternary ammonium siliconcompounds.

U.S. Pat. No. 3,661,963 to Pepe et al describes quaternary ammoniumsalts of chloromethylated silanes or siloxanes which are useful asantistatic agents. These quaternary ammonium salts are prepared byreacting a tertiary amine of the formula R₃ N, where R is a monovalentorganic radical, with a chloromethylarylsilane or achloromethylaralkylsilane.

U.S. Pat. No. 3,734,763 to Plueddemann describes cationic unsaturatedamine functional silane coupling agents which can be applied to glassfibers to minimize the build-up of static charge on the fibers. Theseamine functional silane coupling agents can be prepared by reactingconjugated unsaturated alkyl halides with an aminofunctional silane.

In contrast to the quaternary ammonium silicon compounds describedabove, the quaternary ammonium-functional silicon compounds of thepresent invention impart antistatic properties to textile materialswhich withstand repeated washings. Moreover, the quaternaryammonium-functional silicon compounds, especially the quaternaryammonium-functional organopolysiloxanes are prepared from commerciallyavailable materials.

Therefore, it is an object of this invention to provide a process forpreparing novel quaternary ammonium-functional silicon compounds.Another object of this invention is to provide quaternaryammonium-functional silicon compounds which impart antistatic propertiesto textile materials. Still another object of this invention is toprovide quaternary ammonium-functional silicon compounds which adhere totextile materials after repeated washings. A further object of thisinvention is to provide a process for preparing quaternaryammonium-functional organopolysiloxanes which impart antistaticproperties to textile materials.

SUMMARY OF THE INVENTION

The foregoing objects and others which will become apparent from thefollowing description are accomplished in accordance with thisinvention, generally speaking, by providing a process for preparingquaternary ammonium-functional silicon compounds which comprisesreacting carboxylic acid-functional quaternary ammonium compounds withcarbinol-functional silicon compounds. These compositions may be appliedto textile fibers to provide antistatic properties.

DETAILED DESCRIPTION OF THE INVENTION

The carboxylic acid-functional quaternary ammonium compounds which arereacted with the carbinol-functional compounds may be represented by theformulas ##STR1## wherein R which may be the same or different is amonovalent hydrocarbon radical having from 1 to 22 carbon atoms, R¹ is ahydrocarbonoxy radical represented by the formula

    --(C.sub.n H.sub.2n O).sub.r,

in which the terminal carbon atom is linked to the nitrogen atom, R²which may be the same or different is a divalent hydrocarbon radicalselected from the group consisting of (CH₂)_(y), CH═CH, a cyclicdivalent hydrocarbon radical selected from the group consisting of C₃H₄, C₄ H₆, C₅ H₈, C₆ H₄, C₆ H₈, C₆ H₁₀ and C₁₀ H₆, or a bicyclic radicalselected from the group consisting of C₇ H₈, C₇ H₁₀, C₈ H₁₀ and C₈ H₁₃,R³ is a divalent hydrocarbon radical having from 2 to 10 carbon atoms, Xis an anionic radical, a is a number of from 1 to 4, b is a number offrom 0 to 3, c is a number of from 1 to 3, d is a number of from 0 to 2,in which the sum of a+b cannot exceed 4 and the sum of c+d cannot exceed3, n is 2, 3 or 4, r is a number of from 1 to 50, and y is a number offrom 0 to 10.

The carboxylic acid-functional quaternary ammonium compounds may beprepared by reacting carbinol-functional quaternary ammonium compoundsof the formulas ##STR2## where R, R¹, R³, X, a and c are the same asabove, with dicarboxylic acids or cyclic anhydrides thereof to form thecarboxylic acid-functional quaternary ammonium compounds.

The resultant carboxylic acid-functional quaternary ammonium compoundsare then reacted with carbinol-functional silicon compounds having unitsof the general formula ##STR3## where R and b are the same as above, R⁴is selected from the group consisting of saturated divalent hydrocarbonradicals and divalent hydrocarbonoxy radicals in which the oxygen is inthe form of an ether linkage.

The carbinol-functional silicon compounds may also contain siloxaneunits of the formula ##STR4## where R and b are the same as above, inwhich the siloxanes may be endblocked with silanol, alkoxy, aryloxy ortriorganosiloxy groups.

The carboxylic acid-functional quaternary ammonium compounds are reactedwith the carbinol-functional silicon compounds at a temperature of fromabout 0° C. up to about 175° C. and more preferably from about 25° C. toabout 140° C. It is preferred, although it is not essential, that thereaction be conducted in the presence of a non-protic solvent. Suitableexamples of non-protic solvents are aliphatic hydrocarbons such ashexane and heptane; aromatic hydrocarbons such as benzene, toluene andxylene; ethers such as diglyme and diethyl ether; chlorinatedhydrocarbons such as, 1,1,1 trichloroethane, perchloroethane and carbontetrachloride.

Although the reaction time may vary over a broad range, it is preferredthat the reaction time be limited when the reaction temperature is aboveabout 100° C. in order to avoid degradation of the quaternary ammoniumcompound.

The mole ratio of the carboxylic acid group linked to the quaternaryammonium compound to carbinol group linked to the silicon compound mayvary over a wide range, e.g., from about 4:1 to 1:30, with the provisothat at least one carboxylic acid group is reacted with one carbinolgroup.

After the completion of the reaction the solvent may be removed at atemperature of from about 25° to 150° C., preferably at reducedpressure.

The reaction between the carboxylic acid-functional quaternary ammoniumcompound and carbinol-functional silicon compound forms an ester andwater. The water by-product may be removed either by vacuum stripping oras an azeotrope when the reaction is conducted in the presence of anon-protic solvent.

A catalyst may be employed to accelerate the reaction between thecarboxylic acid-functional quaternary ammonium compound and thecarbinol-functional silicon compound. Examples of suitable catalysts arebases such as alkali metal hydroxides and alkoxides; titanates such astitanium tetrachloride and organic tin compounds such as dibutyltindilaurate, organic acids having a pKa value of less than 1.0 andinorganic acids. Generally, a catalyst level of from about 0.1 percentto 10 percent, based on the weight of the reactants will accelerate thereaction.

The carbinol-functional silicon compounds may be prepared, for example,by reacting silanes containing at least one unsaturated alkoxy group,such as triorganoalkenyloxysilanes, e.g., trimethylallyloxysilanes witha silicon compound containing at least one Si-bonded hydrogen in thepresence of a platinum catalyst. The resultant product containing, forexample, the trimethylpropoxy group, is then reacted with water to formthe carbinol-functional group.

The carboxylic acid-functional quaternary ammonium compounds employed inthis invention may be prepared by reacting dicarboxylic acids or cyclicanhydrides thereof with the carbinol-functional quaternary ammoniumcompounds at a temperature of from about 50° to 175° C. and morepreferably at a temperature of from about 75° to 150° C. Generally, itis preferred that the reaction be conducted in the presence ofnon-protic solvents.

The same non-protic solvents described above may be used in preparingthe carboxylic acid-functional quaternary ammonium compounds. Thesolvent may be removed in vacuum at 25° to 150° C.

The mole ratio of cyclic anhydride to carbinol group bonded to thequaternary ammonium compounds may vary over a wide range. For example,the mole ratio of cyclic anhydride to carbinol group may range form 1:1to 1:4 with the proviso that at least one carbinol group is reacted withthe cyclic anhydride molecule.

When dicarboxylic acids are reacted with the carbinol-functionalquaternary ammonium compounds, then it is preferred that the reaction beconducted in the presence of a non-protic solvent which is capable ofazeotroping with the water byproduct. The solvent may then be removed invacuum at 25° to 150° C.

The same catalysts may be employed to accelerate the reaction betweenthe dicarboxylic acid and the carbinol-functional quaternary ammoniumcompounds as was used to promote the reaction between the carboxylicacid-functional quaternary ammonium compound and the carbinol-functionalsilicon compound. Generally, a catalyst level of from about 0.1 percentto 10 percent, based on the weight of the reactants will accelerate thereaction.

The mole ratio of carboxylic acid group to carbinol group bonded to thequaternary ammonium compounds may vary over a wide range. For example,the mole ratio of carboxylic acid group to carbinol group may range fromabout 8:1 to 2:1, with the proviso that at least one carboxylic acidgroup is reacted with one carbinol group.

Suitable examples of dicarboxylic acids which may be employed to formthe carboxylic acid-functional quaternary ammonium compounds are oxalicacid, malonic acid, succinic acid, glutaric acid, phthalic acid, adipicacid, pimelic acid, suberic acid, azelaic and sebacic acid. Suitableexamples of cyclic anhydrides are succinic anhydride, glutaconicanhydride, maleic anhydride, 1,2 cyclohexane dicarboxylic anhydride,1-cyclohexene-1,2-dicarboxylic anhydride, 3-cyclohexene-1,2-dicarboxylic anhydride, 4-cyclohexene-1, 2-dicarboxylic anhydride,1,8-naphthalic acid anhydride and phthalic anhydride.

The carbinol-functional quaternary ammonium compounds may be prepared byconventional processes known in the art. For example, they may beprepared by reacting an alkyl halide containing at least one carbinolgroup with an amine or ammonia.

The counter-ion in the carbinol-functional quaternary ammonium compoundcan be any anionic group. Suitable examples of anionic groups arehalogens, such as chlorine, fluorine, iodine and bromine; methyl sulfateand phosphate anions.

Suitable examples of monovalent hydrocarbon radicals represented by Rare alkyl radicals, such as methyl, ethyl, propyl, butyl, hexyl, octyl,decyl, dodecyl, hexadecyl, octadecyl radicals; alkenyl radicals such asthe vinyl, allyl as well as octadecenyl radicals; aryl radicals such asphenyl and naphthyl radicals; alkaryl radicals such as, tolyl, xylyl andethylphenyl radicals; cycloalkyl radicals such as cyclobutyl, cyclohexyland cyclodecyl radicals; aralkyl radicals such as benzyl, 2-phenylethyland 2-phenylpropyl radicals.

Examples of suitable divalent hydrocarbonoxy radicals represented by R¹are radicals of the formula

    (C.sub.n H.sub.2n O).sub.r

where the terminal carbon atom is linked to the nitrogen atom, r is anaverage number of from 1 to 50, and n is 2, 3, or 4.

Examples of suitable divalent hydrocarbon radicals represented by R¹,and R² having up to 10 carbon atoms are methylene, ethylene,trimethylene, tetramethylene, pentamethylene, hexamethylene,octamethylene and decamethylene radicals. Examples of divalent arylradicals are phenylene, cyclohexenylene and naphthenylene. Examples ofsuitable divalent hydrocarbon radicals represented by R³ are ethylene,trimethylene, tetramethylene, pentamethylene, hexamethylene,octamethylene and decamethylene radicals.

Examples of suitable divalent radicals represented by R⁴ are hydrocarbonradicals such as ethylene, trimethylene, hexamethylene, andoctamethylene radicals and hydrocarbonoxy containing radicals of theformula

    (C.sub.2 H.sub.4 O).sub.r (CH.sub.2).sub.z, (C.sub.3 H.sub.6 O).sub.r (CH.sub.2).sub.z and (C.sub.4 H.sub.8 O).sub.r (CH.sub.2).sub.z

where r is from 1 to 50 and z is a number of from 1 to 10.

The quaternary ammonium-functional silicon compounds may be mixed withvarious diluents. Examples of suitable diluents are organic solventssuch as alcohols, e.g., ethanol and 1-propanol; aliphatic hydrocarbonsolvents such as heptane and iso-octane; aromatic hydrocarbon solventssuch as toluene and xylene and chlorinated hydrocarbon solvents such aschloroform and 1,1,1-trichloroethane. Other diluents areorganopolysiloxanes having a viscosity up to 100,000 mPa.s at 25° C.,such as hexamethyldisiloxane, and dimethylpolysiloxanes; cyclicsiloxanes such as octamethylcyclotetrasiloxane; organofunctionalpolysiloxanes such as aminofunctional polysiloxanes, mercaptofunctionalpolysiloxanes and carboxylic acid-functional polysiloxanes. Also, thequaternary ammonium-functional silicon compounds may be combined with adiluent such as water.

The quaternary ammonium-functional silicon compounds of this inventionmay be used to treat textile materials to impart antistatic propertiesthereto.

These quaternary ammonium-functional silicon compounds may be applied totextile fabrics in concentrated form or in the presence of a diluent.The amount of quaternary ammonium-functional silicon compound present inthe diluent may range from about 0.25 to 99 percent, preferably fromabout 2 to 50 percent by weight based on the weight of the quaternaryammonium-functional silicon compound and the diluent.

The quaternary ammonium-functional silicon compounds of this invention,and if desired other substances, may be applied to all textilematerials, preferably organic textile materials on whichorganopolysiloxanes have been or could have been applied heretofore.Examples of such textile materials are wool, cotton, rayon, hemp,natural silk, polypropylene, polyethylene, polyester, polyurethane,polyamide, cellulose acetate, polyacrylonitrile fibers, and mixtures ofsuch fibers. The textile materials may consist of staple fibers ormonofilaments.

The quaternary ammonium-functional silicon compounds of this inventionand other substances, if desired, may be applied to the textilematerials by any means known in the art, such as by spraying, immersion,padding, calendering or by gliding the fibers across a base which hasbeen saturated with the quaternary ammonium-functional silicon compoundsof this invention and other materials, if desired.

Generally, the solids add-on is in the range of from 0.001 to 20 percentand more preferably from about 0.05 to 10 percent, based on the originalweight of the textile material.

After the textile material has been treated, it is dried at an elevatedtemperature, e.g., from about 50° to 200° C. for a brief period of timee.g., from about 3 to 15 minutes.

Specific embodiments of this invention are further illustrated in thefollowing examples in which all parts and percentages are by weightunless otherwise specified.

EXAMPLE 1

(a) Preparation of carboxylic acid-functional quaternary ammoniumcompound.

To a reactor containing 320 parts of a carbinol-functional quaternaryammonium compound represented by the formula ##STR5## is added 150.8parts of succinic anhydride and 925 parts of toluene and heated for 10hours at 100° C. The toluene is then removed in vacuum for 2 hours at100° C. The resultant product is a dark, amber, gum-like polymer havingan acid content of 3.25 milliequivalents/g (calculated 3.3milliequivalents/g). Infrared analysis of the product shows the absenceof succinic anhydride.

(b) Preparation of quaternary ammonium-functional silicon compound:

To a reactor containing 235 parts of the above carboxylicacid-functional quaternary ammonium compound is added 852 parts of acarbinol-functional silicone fluid represented by the formula ##STR6##and heated in vacuum at 100° C. for 24 hours. About 12 parts of waterare collected in a flask cooled in dry ice. The resultant product is anamber, opaque gum having a nitrogen content of 0.45 percent (calculated0.48 percent) and a hydrolyzable chloride content of 1.1 percent,(calculated at 1.2 percent).

EXAMPLE 2

(a) Preparation of a carboxylic acid-functional quaternary ammoniumcompound:

To a reactor containing 320 parts of a carbinol-functional quaternaryammonium compound having the formula ##STR7## is added 365.2 parts of1,12-dodecanedioic acid and 925 parts of xylene and refluxed until about27 parts of water are azetroped off. The reaction mixture is then cooledto room temperature. The acid content of the resultant solution is 0.9milliequivalents/g (calculated 0.96 milliequivalents/g). The chloridecontent is 1.6 percent (calculated 1.8 percent) and the nitrogen contentof the resultant product is 0.6 percent, (calculated 0.7 percent).

(b) Preparation of quaternary ammonium-functional silicon compound.

To a reactor containing 625 parts of the carboxylic acid-functionalquaternary ammonium compound and 925 parts of xylene prepared in Example2(a) above, is added 1841 parts of a carbinol functionalpolydimethylsiloxane represented by the formula ##STR8## and refluxeduntil about 27 parts of water are azeotroped off. The product isstripped at 150° C. for 3.0 hours to remove the xylene. The resultantproduct is an amber gum having a nitrogen content of 0.39 percent(calculated 0.44 percent) and a chloride content of 1.0 percent,(calculated 1.1 percent). Infrared analysis indicates that the productis a quaternary ammonium-functional silicon compound.

EXAMPLE 3

(a) Preparation of a carboxylic acid-functional quaternary ammoniumcompound.

To a reactor containing 320 parts of a carbinol-functional quaternaryammonium compound having the formula ##STR9## is added 232 parts ofadipic acid and 925 parts of xylene and refluxed until about 27 parts ofwater are azeotroped off. The reaction mixture is then cooled to roomtemperature. The acid content of the resultant solution is 1.0milliequivalents/g, (calculated 1.08 milliequivalents/g).

(b) Preparation of quaternary ammonium-functional silicon compound.

To a reactor containing 520 parts of the carboxylic acid-functionalquanternay ammonium compound and 925 parts of xylene prepared in Example3(a) above, is added 920.5 parts of a carbinol-functionalpolydimethylsiloxane represented by the formula ##STR10## and refluxeduntil about 27 parts of water are azeotroped off. The product is vacuumstripped at 150° C. for 3.0 hours to remove the xylene. The resultantproduct is an amber, opaque liquid having a viscosity of about 40,000mPa.s at 25° C. The product contains about 0.7 percent nitrogen(calculated 0.75 percent) and has a chloride content of 1.8 percent(calculated 1.9 percent).

EXAMPLE 4

(a) Preparation of carboxylic acid-functional quaternary ammoniumcompound.

To a reactor containing about 129.8 parts of a carbinol-functionalammonium compound having the formula ##STR11## is added about 120, partsof succinic anhydride and heated at 100° C. for 10 hours. The resultantquaternary ammonium compound has a chloride content of 5.1 percent(calculated 5.7 percent). It has a nitrogen content of 2.0 percent(calculated 2.2 percent), and an acid content of 0.5 milliequivalents/g(calculated 0.5 milliequivalents/g).

(b) Preparation of quaternary ammonium-functional silicon compound.

To a reactor containing 247 parts of the carboxylic acid-functionalquaternary ammonium compound prepared in accordance with Example 4(a)above is added 5,664 parts of a carbinol-functional polydimethylsiloxanerepresented by the formula ##STR12## and heated at 100° C. in vacuum for18 hours. About 20 parts of water is collected in a flask cooled in dryice. The resultant product is a viscous, amber liquid having a nitrogencontent of 0.09 percent (calculated 0.09 percent) and a chloride contentof 0.2 percent (calculated 0.24 percent).

EXAMPLE 5

(a) Preparation of carboxylic acid-functional quaternary ammoniumcompound.

To a reactor containing 300 parts of a carbinol-functional quaternaryammonium compound having the formula ##STR13## is added 210 parts ofphthalic anhydride and 925 parts of xylene and heated for 10 hours at100° C. The resultant solution is an amber liquid having an acidequivalent of 0.95 milliequivalents/g (calculated 0.99milliequivalent/g).

(b) Preparation of quaternary ammonium-functional silicon compound.

To a reactor containing 510 parts of the carboxylic acid-functionalquaternary ammonium compound and 925 parts of xylene prepared in Example5(a) above, is added 3445 parts of a carbinol-functionalpolydimethylsiloxane having the formula ##STR14## and refluxed untilabout 24 parts of water are azeotroped off. The product is vacuumstripped at 150° C. for 3.0 hours to remove the xylene. The resultantliquid product has a nitrogen content of 0.2 percent (calculated 0.25percent), and a chloride content of 0.59 percent (calculated 0.64percent). Infrared analysis indicates that the product is a quaternaryammonium-functional silicone fluid.

EXAMPLE 6

(a) Preparation of carboxylic acid-functional quaternary ammoniumcompound.

The procedure of Example 5(a) is repeated except that 309 parts of acarbinol-functional quaternary ammonium compound having the formula##STR15## is substituted for the carbinol-functional quaternary ammoniumcompound prepared in Example 5(a). The resultant solution is an amberliquid having an acid equivalent of 1.0 milliequivalents/g (calculated0.98 milliequivalents/g).

(b) Preparation of quaternary ammonium-functional silicon compound.

The procedure of Example 5(b) is repeated except that the carboxylicacid-functional quaternary ammonium compound prepared in accordance withExample 6(a) is substituted for the carboxylic acid-functionalquaternary ammonium compound prepared in Example 5(b). The resultantliquid product has a nitrogen content of 0.23 percent (calculated 0.25percent) and an acetoxy content of 0.94 percent (calculated 1.06percent) as determined by Nuclear Magnetic Resonance analysis. Infraredanalysis shows that the product is a quaternary ammonium-functionalpolydimethylsiloxane.

EXAMPLE 7

(a) Preparation of carboxylic acid-functional quaternary ammoniumcompound.

The procedure of Example 5(a) is repeated except that 839 parts of acarbinol-functional quaternary ammonium compound having the formula##STR16## is substituted for the carbinol-functional quaternary ammoniumcompound prepared in Example 5(a). The resultant amber colored solutionhas an acid equivalent of 0.8 milliequivalents/g (calculated 0.72milliequivalents/g).

(b) Preparation of quaternary ammonium-functional silicon compound.

The procedure of Example 5(b) is repeated except that the carboxylicacid-functional quaternary ammonium compound prepared in Example 7 (a)is substituted for the carboxylic acid-functional quaternary ammoniumcompound prepared in Example 5(a). The resultant liquid product has anitrogen content of 0.18 percent (calculated 0.22 percent) and achloride content of 0.48 percent (calculated 0.56 percent). Infraredanalysis indicates that the product is a quaternary ammonium-functionalpolydimethylsiloxane.

EXAMPLE 8

The procedure of Example 5(a) is repeated except that glutaconicanhydride is substituted for the phthalic anhydride. A carboxylicacid-functional quaternary ammonium compound is obtained

The resultant carboxylic acid quaternary ammonium-functional compound isthen reacted with the carbinol-functional polydimethylsiloxane inaccordance with the procedure described in Example 5(b). A quaternaryammonium-functional polydimethyl-siloxane is recovered.

EXAMPLE 9

The procedure of Example 5(a) is repeated except that 1,2-cyclohexanedicarboxylic anhydride is substituted for the phthalic anhydride. Acarboxylic acid-functional quanternary ammonium compound is obtained.

The resultant carboxylic acid-functional quanternary ammonium compoundis then reacted with the carbinol-functional polydimethylsiloxane inaccordance with the procedure described in Example 5(b). A quaternaryammonium-functional polydimethylsiloxane is recovered.

EXAMPLE 10

The antistatic properties of the quaternary ammonium-functional siliconcompounds prepared inthe above Examples are determined by applying a 5percent solution of the compounds prepared in the above Examples in2-propanol on 100 percent polyester fabric. The treated fabric is driedfor 60 seconds at 175° C. The surface resistivity of the treated fabricis shown in the following table.

    ______________________________________                                        Composition             Surface Resistivity                                   Example No.  Fabric     Ohms                                                  ______________________________________                                        1            Dacron T-54                                                                              1.75 × 10.sup.10                                2            Dacron T-54                                                                              3.5 × 10.sup.10                                 3            Dacron T-54                                                                              2.5 × 10.sup.10                                 4            Dacron T-54                                                                              3.5 × 10.sup.11                                 5            Dacron T-54                                                                              2.4 × 10.sup.10                                 6            Dacron T-54                                                                              2.7 × 10.sup.10                                 7            Dacron T-54                                                                              9.5 × 10.sup.9                                  8            Dacron T-54                                                                              2.25 × 10.sup.10                                9            Dacron T-54                                                                              3.25 × 10.sup.11                                None         Dacron T-54                                                                              1.02 × 10.sup.15                                ______________________________________                                    

What is claimed is:
 1. A process for imparting antistatic properties totextile materials which comprises applying a composition obtained fromthe reaction of a carboxylic acid-functional quaternary ammoniumcompound and a carbinol-functional silicon compound to a textilematerial and thereafter heating the textile material to an elevatedtemperature.
 2. The process of claim 1, wherein the carboxylicacid-functional quaternary ammonium compound is selected from the groupconsisting of compounds having the formulas ##STR17## in which R is amonovalent hydrocarbon radical having from 1 to 22 carbon atoms, R¹ is ahydrocarbonoxy radical having the formula --(C_(n) H_(2n) O)_(r), R² isa divalent hydrocarbon radical selected from the group consisting of(CH₂)_(y), CH═CH and cyclic divalent hydrocarbon radicala selected fromthe group consisting of C₃ H₄, C₄ H₆, C₅ H₈, C₆ H₄, C₆ H₈, C₆ H₁₀, C₁₀H₆, and a bicyclic radical selected from the group consisting of C₇ H₈,C₇ H₁₀, C₈ H₁₀ and C₈ H₁₃, R³ is a divalent hydrocarbon radical havingfrom 2 to 10 carbon atoms, X is an anionic radical, a is a number offrom 1 to 4, b is 0, 1, 2 or 3, c is 1, 2 or 3, d is a number of from 0to 2, in which the sum of a+b cannot exceed 4, and the sum of c+d cannotexceed 3, n is 2, 3 or 4, r is a number of from 1 to 50 and y is anumber of from 0 to
 10. 3. The process of claim 1, wherein thecarbinol-functional silicon compound contains at least one unit of theformula ##STR18## in which R is a monovalent hydrocarbon radical havingfrom 1 to 22 carbon atoms, R⁴ is a radical selected from the groupconsisting of a saturated divalent hydrocarbon radical having up to 10carbon atoms and a divalent hydrocarbonoxy radical in which the oxygenis in the form of an ether linkage and b is 0, 1, 2 or
 3. 4. The processof claim 3, wherein the carbinol-functional silicon compound contains atleast one unit of the formula ##STR19## where R is a monovalenthydrocarbon radical having from 1 to 22 carbon atoms and b is 0, 1, 2 or3.
 5. The process of claim 2, wherein the composition is mixed with adiluent which is a solvent for the composition.
 6. The process of claim5, wherein the diluent is water.
 7. The process of claim 5, wherein thediluent is an organopolysiloxane.
 8. The process of claim 5, wherein thediluent is an organofunctional polysiloxane selected from the groupconsisting of an aminofunctional polysiloxane, a mercaptofunctionalpolysiloxane and a carboxylic acid functional polysiloxane.
 9. Theprocess of claim 1, wherein the treated textile material is heated to atemperature up to about 200° C.